Amino-triazol derivatives



Nov. 30,

III

III

IKE

III

OOOOOOOOVIOOOMO 1965 M. J. KOOPMANS ET AL AMINO-TRIAZOL DERIVATIVESOriginal Filed April 22, 1958 Pky Toxic.

s Mi \6: Chloro GOO-Q00 Tctrmychus urtico: Koch T A a L E It INVENTmnrmus .1. KOOQHNS F I 8 I .mcouss MELTZER nsuosnmus o. HUISfiANssnunnous a. VAN DE so xoaus WELLINGA United States Patent 10 Claims.for. 167-33) The invention relates to a method of producing newamino-triazol derivatives. From laboratory experiments it has been foundthat these products are suitable for combating noxious organisms.

This application is a division of our copending application Serial No.730,130, filed April 22, 1958, now US. Patent 3,121,090.

The invention is characterized in that a derivative of an amino-triazolof the general formula:

or of a tautomeric form thereof is produced by suitable methods, inwhich derivative the phosphorous atom is bound to one of the nitrogenatoms of the triazol-ring and in which furthermore R R R and R designatealiphatic hydrocarbon radicals, X a double-bonded oxygenor sulphur atomand R designates a hydrogen atom, an alkyl-, cycloalky1-, aryloraralkyl-group.

The production of the compounds according to the invention isfurthermore characterized in that a compound of the general formula:

a tautomeric form or a salt of either of them is caused to react with acompound of the general formula:

in which formulae R designates a hydrogen atom or an alkyl-,cycloalkyl-arylor aralkyl-group, in which groups one or moresubstituents and/ or unsaturated bonds may be contained, R R R and Rdesignate aliphatic hydrocarbon radicals, X designates a double-bondedoxygenor sulphur atom and Hlg a halide atom, for example a chlorine orbromine atom, so that a product is obtained, in which the hydrogen atombound to nitrogen in the amino-triazol ring is replaced by the bis(N,N-dialkylamido)-phosphorylor thiophosphoryl-group, in such a way thatthe phosphorous atom is bound at a nitrogen atom of the triazol ring.

3,220,922 Patented Nov. 30, 1965 It has been found that reactionproducts with attractive properties are obtained, in particular, if3-amino- 1,2,4-triazol or a derivative thereof according to thedefinition of the invention is used as a starting material, in which Ris an aliphatic hydrocarbon radical having 1 to 8 carbon atoms, a phenylgroup, 4-chloro-phenyl-4-methoxy-phenyl-, carboxy-alkyl-, benzylorstyryl-group. In the phosphorylor thiophosphoryl-compounds R R R and Rare preferably aliphatic hydrocarbon radicals having 1 to 5 carbonatoms, particularly methyl groups. The method is preferably carried outwith bis (N,N-di alkyl-amido)-phosphorylor thiophosphoryl-chloride.

As a salt of 3-amino-triazol 1,2,4 or of the R -derivative may be used,for example, the hydrochloric acid salt, the sulphuric acid salt or thebisulphate.

In the cases, in which the starting material is 3-aminotriazol 1,2,4 theR derivative thereof or the salts of an acid, for example hydrochloricacid or sulphuric acid or the bisulphate of one of them, the choice ofthe solvent is primarily determined by the solubility of S-aminotriazol1,2,4 or the R derivative thereof, since the phosphorylorthiophosphoryl-compounds employed in accordance with the invention aresatisfactorily soluble in a great many of the conventional solvents.

In these cases suitable solvents are: liquid aliphatic hydro-carbons,for example petroleum ether, ligroin, hexane, cyclohexane, aromatichydrocarbons, for example, benzene, toluene, xylene; aliphatic ethers,for example diethyl ether, methyl-ethyl ether, di-iso-propyl ether,tetrahydrofurane, tertiary amines, for example, tri-ethylamine pyridinepicolines, lutidines or collidines or mixtures thereof. As a suitablesolvent may be mentioned acetonitril. If desired, lower aliphaticketones may be used, for example, acetone or methyl-ethyl ketone, but inthis case, it should be considered that these solvents can react withthe triazol-derivative whilst forming a Schifis base. Other solvents areethyl-acetate, ethyl-formate, nitrobenzene, carbon tetrachloride anddi-methyl-formamide.

In general, amino-triazol and derivatives thereof, of which the group Rcontains more than 5 carbon atoms, are better soluble in liquids oflower polarity. For this reason, when using these amino-triazolderivatives, it is to be preferred to use aliphatic or aromatichydrocarbons or ethers over the other aforesaid of higher polarity. Thelatter group of solvents may be often used successfully, if anamino-triazol is used as a starting material, in which R is hydrogen ora carbon chain having less than 5 carbon atoms. Mention may be made ofacetonitril and furthermore a liquid tertiary amine, preferably pyridineor the homologues thereof: the picolines, lutidines and collidines.

It should otherwise be noted that, for a successful reaction, it is,indeed, desirable but not necessary that the two reaction componentsshould be in a completely dissolved state from the start of the process.The reaction is also accomplished, if, for example, the triazolderivative is contained partly in the diluent in a roughly dispersedstate.

It is furthermore important to carry out the reaction in the presence ofan acid binder. The amino-triazol or R -derivative thereof, used asstarting material, may serve as such, in which case an excess quantityof this compound is employed.

A group of acid binders which may be successfully used, are amines andparticularly tertiary amines, for example of the group consisting oftrialkylamines, N,N- dialkylanilines; trimethylamine, triethylamine,diethylaniline and furthermore pyridine or homologues thereof, forexample the picolines, lutidines or collidines and furthermoretriethanolamine. As a primary amine use may be made of ethanolamine, asa secondary amine for example diethanolamine. Even the amino-triazol:advisable to purify the reaction product.

derivative, which is the starting material and which is obtained by thereaction according to the invention may operate as an acid binder. Ingeneral, use will be made of a quantity of acid binder which isequivalent to the quantity of hydrogen halide set free during thereaction but there is no objection to use a larger quantity.

If an excess quantity of 3-amino-l,2,4 triazol or an anacid binder thereaction is preferably carried out at a temperature lying between and 80C., for example, at a temperature of about 40 C. to 70 C.

After the termination of the coupling reaction between the aminotriazolor an R -derivative thereof with the phosphorylhalide or thethio-phosphorylhalide it is This may be carried out by removing thesolvent, for example by evaporation in vacuo. The residue, whichcontains apart from the reaction product the hydrogen halide salt of theacid binder and, as the case may be, unchanged starting material maythen be extracted with a suitable solvent, for example an aromatic oraliphatic hydrocarbon, such as toluene, xylene, benzene, hexane, pe-

troleum ether, ligroine or an aliphatic ether, for example, ethyl etheror dimethyl ether. From the extract thus obtained, which issubstantially free from the salt of the employed acid binder, thepurified reaction product may be obtained by conventional purifyingmethods, for example, recrystallisation. If the amino-triazol derivativecontained a group R with more than 4 carbon atoms, the aforesaid extractmay be purified by washing it with water. With this treatment an excessquantity, if any,

of phosphorylor thiophosphoryl-compound, as well as the acid binder, ifat least the latter compound is soluble in water, are removed.

It has furthermore been found that very satisfactory .results areobtainable when using a different group of acid binders. This groupcomprises metal compounds and ammonium compounds, which are suitable tobind the hydrogen halide set free during the reaction according to theinvention; with particular advantage may be .used those ofalkaline-earth metals, for example, those of calcium and barium and,particularly those of alkaline metals, for example those of sodium andpotassium. As metal compounds may be used oxides, hydroxides,carbonates, bicarbonates, alcoholates and metal salts of carboxylicacids for example acetates and propionates, for instance sodium-,potassium,- calcium-, magnesiumand zinc-hydroxide, calcium-, bariumandzinc-oxide, sodiumand potassium-carbonate and -bicarbonate, magnesium-,calciurnand barium-carbonate, sodiumand potassium-alcoholates andsodium-acetate. As ammonium compounds use may be made of ammonia,ammonium-carbonate and -acetate.

Suitable acid binders in accordance with the method of the invention arethe metal hydroxides, particularly calcium-- and bariumand particularlysodiumand potassium-hydroxide. Very satisfactory acid binders are,furthermore, the alkaline metal alcoholates, such as sodium, andpotassium-methanolate and ethanolate.

With the reaction according to the invention of 3- amino-triaZol-1,2,4or the R -derivative thereof with a phosphorylor thiophosphoryl halidein the presence of a metal compound as an acid binder, the metal halideis separated out. This reaction may be carried out in different ways.

A suitable method is that in which as an acid binder use is made of analkaline metal alcoholate. In this case, preferably the3-amino-triazol-1,2,4 or the R -derivative thereof is dissolved in asolution of an alkaline metal alcoholate in anhydrous alcohol,particularly a lower alcohol and more particularly methanol or ethanol,to which is added the phosphoryl halide or thiophosphoryl halidederivative. The alcoholate may be formed, for example,

by dissolving the alkaline metal in the alcohol to be used as a solvent.

When using a metal hydroxide as an acid binder, a suitable method forthe reaction according to the invention consists in that the3-amino-triazol-1,2,4 or the R derivative thereof is dissolved in apolar organic solvent, in which the metal hydroxide is dissolved, orsuspended in a finely divided state, after which the phosphoryl halideor the thiophosphoryl halide derivative is added.

The metal hydroxides are particularly those of sodium and potassium andthose of calcium, and barium. When using sodiumor potassium-hydroxide,it is advantageous to use, as a polar organic solvent, a lower alcohol,for example methanol or ethanol, since these hydroxides are soluble inthese alcohols. The reaction is then carried out in a homogeneousmedium.

It has been a surprise to find that the reaction according to theinvention may yield, moreover, very satisfactory results of, as an acidbinder, use is made of aqueous alkaline-earthor alkaline-hydroxides. Onemethod which yields particularly satisfactory products according to theinvention in substantially theoretical quantities is that in which the3-amino-triazol-l,2,4 or the R derivative thereof is dissolved in amixture of a polar organic solvent, preferably a lower alcohol, forexample methanol or ethanol and, for example, the theoretically requiredquantity of alkali-hydroxide, for example as a 30 to 50% by weightsolution is dissolved in water, to which the phosphoryl halide or thethiophosphoryl halide is added. Particularly satisfactory results areobtained by using a mixture of methanol or ethanol and 30 to 50% aqueoussolution of sodiumand potassium hydroxide. In these cases, yields of toof the desired product may be obtained. The term theoretic-ally requiredquantity of alkalihydroxide is to be understood to mean herein thequantity required to bind the maximum quantity of hydrogen halide setfree during the reaction.

The use of alkali-metal hydroxides as acid binders and the use of loweralcohols as solvents are advantageous to the technical performance ofthe reaction, since in this case the reaction takes place in ahomogeneous medium. An advantage of the use of an aqueous solution ofalkalihydroxide over that of solid alkali-hydroxide is that in the firstcase a homogeneous solution is obtained immediately after mixing. Whenusing solid alkali-hydroxide some time passes before it is dissolved.

For carrying out the reaction according to the invention, in which metalcompounds are used as acid binders, use is preferably made of polarsolvents, for example alcohols such as propanol, isopropanol, butanol,secondary butanol and isobutanol particularly, methanol or ethanol andketones such as acetone and methyl-ethyl ketone or acetonitril. Evennon-polar solvents such as aliphatic hydrocarbons and aromatichydrocarbons, for example benzene, toluene or xylene may be used. Since,however, the metal compound to be used as an acid binder is solubleherein only with difficulty, the reaction is performed less smoothly inthese cases.

The yields of compounds according to the invention usually exceed, whenmetal compounds are used as acid binders and when polar solvents areused, as a rule those obtained when amines are used as acid binders.These higher yields, which may attain the theoretical values, are to beascribed, inter alia, to the simplicity of the working up andpurification of the reaction product and, probably particularly to thesmooth reaction even at a low temperature, so that no or substantiallyno by-products will be formed.

. It is known that the phosphoryl chlorides and thiophosphorylchlorides, as acid chlorides, are sensitive to the effect of waterandmetal hydroxide solutions.

Quite contrary to the expectations it has now been found that evensatisfactory results may be obtained, when the reaction according to theinvention is carried out with a suspension of 3-amino-triazol-1,2,4, orthe R derivative thereof in a concentrated aqueous solution orsuspension of an alkalior earth-alkali-hydroxide.

When carrying out the reaction according to the invention in a 50%aqueous sodiumor potassium-hydroxide solution, yields of 70 to 80% ofthe desired products were obtained.

With this method the compounds according to the invention, in which Rdesignates an alkyl group with at least 5 carbon atoms or a cycloalkyl-,aralkylor arylgroup, can be separated out in a very simple manner afterthe reaction has terminated, since they separate out in a finelydivided, solid state.

The method according to the invention in which a metal compound is usedas an acid binder, provides, as a rule, a smooth reaction and may becarried out at normal temperature. The reaction temperature ispreferably chosen to be slightly lower, for example between and +10 C.;this particularly obtains, if the reaction is carried out in an aqueousand particularly a homogeneous medium.

It has been found that the method according to the invention, in whichmetal compounds are used as acid binders and the methods in which aminesare used for the same purpose, yield the same products.

3-arnino-triaZol-1,2,4 and R derivatives thereof have a somewhatamphoteric nature. This means that there may exist not only salts of,for example, hydrochloric acid, but also metal salts. Therefore it isnot impossible that, in those cases in which a metal compound, forexample sodium alcoholate as an acid binder, at least partly the sodiumsalt of the employed amino-triazol should be formed, which might reactwith the phosphoryl halide or thio-phosphoryl halide. For example thesodium salt of a 3-amino-triaZol-1,2,4 may be separated out byevaporating an alcoholic solution of sodium alcoholate and a3-amino-triazol-1,2,4 until no alcohol can any longer be removed. If thesodium salt of the 3-aminotriazol-1,2,4 derivative thus obtained issuspended for example in benzene and if the suspension obtained isheated for some time, after the addition of a phosphoryl halide, asatisfactory quantity of a compound according to the invention isobtained.

It should be noted that the amino-triazol and the said derivativesthereof, employed in accordance with the invention, may occur intautomeric forms. This means that the hydrogen atom bound to one of thenuclear nitrogen atoms does not occupy a fixed position. In order to fixthe idea, the amino-triazol or a derivative thereof in accordance withthe present application is assumed to be given by a formula in whichthis hydrogen atom is bound to the nitrogen atom indicated by ring atomnumber 4. In accordance with conceptions expressed in literature thisdoes not mean, however, that this hydrogen atom could not be bound toany of the other atoms of the amino-triazol (J. Org. Chem. XVIII, page196 (1953)).

The tautomerism with amino-triaZol-1,2,4 and R derivatives thereofinvolves that it cannot be stated with the reaction products thereofwith bis (N,N-dialkylamido)-phosphoryl halides, with which of the threenitrogen atoms in the triaZol-ring the phosphoryl-group is bound. Fromthe experiment, which led to the invention, it has been found that witha definite reaction mainly one product is always formed, which has awell-defined melting point, as will be evident from the examples to bedescribed hereinafter.

Of the amino-triazol derivatives to be used in accordance with theinvention are known the compounds in R5=H, CH3, C2H5, C3H7, iSO-CgHq,iSQ'C4IIg, npentyl, n-hexyl and phenyl. The further compounds in whichR; may be, for example, butyl, heptyl, aralkyl, and so on, may beproduced from an amino-guanidine salt, for example the nitrate,bisulphate or sulphate and a carboxylic acid of the formula R COOH orthe corresponding acid halide, preferably the acid chloride. For theproduction of the amino-triazol itself the principle of this method isdescribed in Organic Synthesis 26, page 11. The bis- 5dialkyl-phosphorylhalide and the corresponding thiocompounds may beproduced by a method as indicated in the German patent specification No.900,814.

In accordance with the invention it has now been found that the productsobtained by the method according to the invention have, as is shown bylaboratory experiments, an activity against noxious organisms,especially against particular fungi-insects and, moreover, red spidermites.

It has particularly been found that many compounds have an activityagainst fungi of the family of the erysiphacenes. To this family belong,for example, the kinds:

(a) Sphaerotheca pannosa (Wa1lr.) Lv (rose),

(b) Erysiphacichoracearum D.C.cucumber, potato, salad, sunflower,tobacco,

(c) Erysiphe polygony D.C.-clover and other leguminoses (d) Uncinulanecator (Schw.) Burrgrape,

(e) Erysiphe gramz'nis D.C.cereals.

(f) Sphaerotheca mors uml (Schw.) Berk-gooseberry,

(g) Podosphaera Ieucotricha (Ell et Everh.) Salm apple, pear. (after thenames of the fungi are indicated after-the plants on which thecorresponding fungi may occur).

Plants, of which the overground parts were sprayed by a productaccording to the invention, were appreciably less affected by theaforesaid fungi than untreated plants.

A protection from the effect of these fungi was also observed when aproduct obtained in accordance with the invention was inserted into theroot system of the plant (emphytical effect).

The said fungicidal elfect is particularly manifest with those reactionproducts which are obtained by causing an amino-triazol, in which thegroup R designates a hydrogen atom, a lower aliphatic radical having 1to 8 carbon atoms or a phenyl group to react with a his(N,N-dimethylamido)-phosphoryl-halide, preferably the chloride.

The experiments by which the aforesaid fungicidal elfect was stated werecarried out as follows.

Young barley plants (Hordeum vulgare) were cultivated at a temperatureof 15 C. to 18 C. in small fiowerpots until the plants had a length ofabout 7 cms. Then solutions of the compounds to be tested in acetone ofdifferent concentrations were sprayed on them. As a rule, a series ofdilutions comprises solutions containing 1000, 100 or 10 mgs. of activecompound per litre. Seven plants in one pot were sprayed simultaneouslywith 0.2 ml. of the solution. The experiment was repeated twice with 7plants each. In total 21 plants were thus treated with the same liquid.Immediately after the treatment with the solution, the plants weredusted with viable sporules of Erysiphe graminis mildew by putting thepots of the whole test series simultaneously under a spaceousbell-glass, into which, by means of a flow of air brushing past stronglyinfected leaves of barley, were distributed the sporules of mildew. Theplants were left to themselves for some time, so that the sporulessettled down uniformly on the plants. The plants were then put into aspace having a temperature of 18 C. to 20 C. and a relative humidity ofabout under a continuous illumination by fluorescent tubes (White light)having an intensity of about 300 Lux. Five days after the inoculationdistinct spots of the mildew fungus had been formed on the test plantsnot treated with an active compound these spots giving off a fair amountof sporules.

The extent of the damage of each plant was expressed by a numeral of theseries 0 to 10, 0 being equal to no affect and 10 meaning that the wholeleaf was covered with stains.

Per concentration21 statementsthe numbers obtained were added.

Since the various substances were tested at difierent dates, which mightaffect the results, the measure of damage of each plant was alwayscompared with the one .obtained when 2,4-d'initro-6 \(1-methyl'heptyl)-1-phenylcrotonate was used as a protecting compound. Those doses weretherefore each time determined which resulted. both with the compound tobe tested and with the phenylcrotonate-derivative, in a protection of50% for the plant. The quotients of these doses are indicated in Table Iin column h. With a higher quotient the fungicidal effect of the testedcompound is, therefore, also higher.

In this table the column a indicates the numeral of the example, inwhich the production of the tested aminotriazol-derivative is described.The columns b to g indicate the kind of substitutents X and R to RColumn It shows the anti-erysiphaceaes effect as compared with 2,4-dinitro-6-(1'-methylheptyl)-1-phenylcrotonate (on barley plants). Incolumn i means that a dose of 30 mgs. of the tested compound per pot (inwhich was cultivated tomato, oat plants, garden beans, chickweed orbeets) produces chlorosis. The reference has the opposite meaning.Column mentions the extent of leaf burning with a spraying of 1% ofaqueous emulsion or a solution of the substance on tomato, oats, gardenbeans, chickweed or beet. means: no damage; is: little damage and is:fairly heavy damage. Column k finally indicates the toxicity forwarmblooded animals. The numbers indicated are the doses in mg./kg. mice(test animals), producing a kill of 50% of the animals upon oralapplication (LD It has furthermore been found that the reaction prodancewith the method of the invention was'determined.

ucts obtained in accordance with the invention have also an activityagainst insects, for example Musca domestica L, Sitophilus granarius L,Leptinotarsa decemlineata Say, Aphis fabae Scop. The active compoundsconstitute both contact poisons and stomach poisons for the insects. Itwas, moreover, stated that leaf-eating and juice-sucking insects on theoverground parts of plants are killed, if the reaction products obtainedin accordance with the invention are inserted into the root system.

This insecticidal effect occurs particularly with those compoundsaccording to the invention which are obtained by the reaction of anamino-triazol derivative, according to the invention, in which Rdesignates a hydrogen atom or an aliphatic hydrocarbon radical having 1to 5 carbon atoms or a phenyl radical, with a his(N,N-dimethylamido)-phosphorylor thiophosphorylhalide.

It has furthermore been found that the products obtained in accordancewith the invention also have an activity against mites (Acari),particularly red spider mites (Tetranychidae). This activity occurs withthe same products of which the insecticidal effect is described above.

The tests to determine the insecticidal and acaricidal effects werecarried out as follows.

Broad bean plants (Vicia faba L) were immersed into an emulsion or asolution of the compound to be tested in water. The compounds wereemployed with the following concentrations: 1000, 300, 100, 30 and 10mgs. per litre (p.p.m.). After the emulsion or the solution had dried onthe plants, they were infected with adult, unwinged female black beanlouse (Aphis fabae Scop). Similar experiments were carried out with bushbean plants (Phaseoli vulgares L,) which were infected with adult femalebean red spider (T etranychus urticae Koch).

At the same time test experiments were carried out, the kill of insectsand red spider mites on the untreated plants is calculated in the killpercentages in accordance with Abbotts formula. This formula goes:

kill percentage, wherein a designates the number of survivors on thecheck plants and b the number of survivors of the object concerned.

With a second series of experiments an emphytical insecticidal effect ofthe substances obtained in accord- With these experiments the same kindsof plants and test animals were used, but in this case the plants werecultivated in paraffined paper beakers, filled with washed sand. Theplants were fed on a so-called Knopps nutrient solution. One litre ofthis liquid contains 0.25 g. of magnesium sulphate, 1.0 g. of calciumnitrate, 0.25 g. of primary potassium phosphate, 0.12 g. of potassiumchloride, a supply of ferrichloride and otherwise water (Koningsberger,Leerboek der algemene Plantkunde, vol. II, page 465 (1942) Amsterdam).

To the beakers was added a solution or an emulsion of the compound to betested in water. The doses employed were: 62.5, 12.5, 2.5, 0.5 and 0.1mgs. of compound per beaker. By screening off the beakers the plantswere protected from the vapour of the compound concerned. Then theplants were infected with plant lice and red spider mites respectively.

With the two series of experiments it was determined how many insects ormites were killed three days after the initiation of the infection. Thekill on check plants was deducted therefrom. When the kill percentagewas to this was indicated by the sign a percentage of less than 90%, butmore than 50% was indicated by i. A kill percentage of less than 50% wasindicated by The results of these experiments are indicated in Table II.In the first left-hand column the Roman ciphers refer to the examples inwhich are described method-s of producing those starting products inwhich the substituents X, R R R R and R are indicated in the followingsix columns. In the head column entitled A phis fabae Scop the subcolumnA relates to the so-called, immersion effect and the subcolumn B to theemphytical insecticidal effect. The numbers 1000, 300, 100, 30, 10indicate the concentrations in mgs. of tested compound per litre(p.p.m.) with which the immersion experiments were carried out. Thenumbers 62.5, 12.5, 2, 5, 0, 5 and 0.1 indicate the quantities of testedcompound (in mgs.) which were added to each beaker with the emphyticaltests. The column T tranychus urn'cue Koch must be understood in asimilar manner.

The term immersion effect is to be understood to relate to theobservations made during the experiments with plants immersed in anemulsion or a solution of the compound to be tested.

A compound obtained in accordance with the invention may be worked up ina conventional manner to obtain a combating means.

To this end they are mixed with solid or liquid carriers or as the casemay be, dissolved therein and, if desired, enriched with dispersionagents, emulsifiers or wetting agents. Preparations thus obtained may besprayed, pulverized or nebulized in air, either as such or emulsified ordispersed in a liquid, for example, Water. Preparations which may beobtained by means of the active compounds are, amongst others, themixable oils, spray powders and dust powders. These forms are referredto only by way of example and should not restrict the invention thereto.

In order to produce mixable oils, the active compound is dissolved in asuitable solvent which is purely soluble with water, to which solutionis added an emulsier. Suitable solvents may be Xylene, toluene, dioxane,petroleum disti-llates rich in aromatic compounds, for example, solventnaphtha, distilled tar oil, tetraline, cyclohexane or mixtures of theseliquids. As emulsifiers may be used alkylphenoxy-polyglycol ethers,poly-oxyethylene-sorbitane esters of fatty acids or poly-oxyethylenesorbitol esters of fatty acids. A plurality of these kinds ofemulsifiers are known under the trade name of Triton, Tween, and Atlox.

The concentration of active compound in the purely water-soluble liquidis not subjected to narrow limits. It may fluctuate, for example,between 2 and 50% by weight. Prior to the use of these solutions, themixable powders.

9 oils are emulsified in water and the emulsion is sprayed out. As arule, the concentration of active compound in these aqueous emulsionslies between 0.01 and 0.5% by weight.

The spraying powders may be produced by mixing and grinding the activecompound with a solid, inert carrier, as a rule, in the presence of adispersion and/ or wetting agent. Prior to use the spraying powders aredispersed in a liquid, preferably in water; the dispersion is sprayedout. It is important that the spraying powder should consist of smallparticles in order to avoid obturation of the aperture of thevolatilizer. It is therefore advisable to use, as a carrier, a fine,pulverulent material. If desired, the mixture of carrier material,active compound and auxiliary substances, if any, is ground.

As a carrier may be used, for example, alumina, diatomaceous earth,kaolin, dolomite, talcum, gipsum, chalk, bentonite, attapulgite,infusorial earth, celith, wood flour, tobacco dust or ground coconutshells. Suitable dispersion agents are lignine sulphonates andnaphthalene sulphonates. As wetting agents may be used faty alcoholsulphates, alkyl-arylsulphonates or fatty-acid condensation products,for example those known under the trade-name of Igepon.

Also in the dust powders the concentration of active compounds is notsubjected to narrow limits; as a rule, the concentration will be chosento lie between and 80% by weight.

The dust powders may be produced by applying the active compound as suchor dissolved in a solvent to a solid carrier. During the use thepreparation thus obtained is pulverized in a dry, finely pulverulentstate, in the air. With a choice of suitable, light carrier materials,these powders may, as an alternative, be produced in the mannerdescribed for the production of spraying As carriers use may be made ofthe products referred to above with the production of spraying powders.Usually, the concentration of active compounds in the dust powders islower than that in the spraying powders or mixable oils, but higher thanthat of the active compounds in dispersion agents or emulsifiers,obtained by diluting spraying powders or mixable oils with liquids. Thedust powders contain frequently 1 to of active compound. .It may beredundant to observe that the mixable oils, spraying powders or dustpowders according to the invention may be produced by mixing two mixableoils (or spraying and dust powders), containing each one of the activecompounds.

EXAMPLE I To a mixture of 134 gs. of 3-amino-triazol-1,2,4 (1.6 mol),194 gs. of collidine (1.6 mol) and 1.6 l. acetonitril is added in drops,at room temperature, 273 gs. of his (N,N dirnethyl amido)phosphorylchloride (1.6 mol). The mixture is then kept at the sametemperature for six hours. During the addition and the further reactionthe mixture is stirred. The acetonitril is then distilled 01? in vacuo.The residue is extracted with benzene. The solution thus obtained isthickened to a small volume. A product is thus crystallized out. Afterrecrystallization from the same solvent a substance is obtained, ofwhich the analysis shows that 1 mol of amino-triazol has reacted with 1mol of the phosphorylchloride derivative.

Yield 52%. Melting point 136.5 to 138 C.

Analysis.Calculated: P=14.19%. Found: P: 14.2%.

Remark: The calculated values of the contents of the various elements inthe products obtained, indicated in this example and in the followingexamples relate always 10 to a compound of 1 mol amino-triazolderivative and 1 mol of the derivative of the phosphoryl halogenide.

EXAMPLE II Whilst stirring to a mixture of 54 gs.5-methyl-3-aminotriazol-1,2,4 (0.55 mol) (Thiele, Heidenreich: Berichte26, page 2599 (1893)), 67 gs. of collidine (0.55 mol) and 300 mls. ofacetonitril is added in drops 94 gs. of bis (N,N-dimethylamido)phosphorylchloride (0.55 mol). The mixture is then stirred further for3.5 hours at a temperature between 60 and 70% C. The acetonitril is thenevaporated in vacuo. The residue is extracted with ether. The etherealsolution is thickened and the crystalline mass obtained isrecrystallized from ligroine and a mixture of petroleum-ether and ether.

The anlysis indicates a reaction between equimolar quantities of theamino-triazol and phosphorylchloride derivatives. Yield 53%. Meltingpoint 91 to 92 C.

Analysis.Calculated: P=13.34%; C.= 36.20%; H =7.38%; N=36.1,9%. Found:P=13.3%; C= 35.66%; 35.40%; H='7.5 3%; 7.51%; N=36.22%; 36.33%.

EXAMPLE III 7.5 gs. of 5-ethyl-3-amino-triazol-l,2,4 mol) (Reilly,Madden, J. Chem. Soc. (1929) page 816), 7.2 gs. of 2,6-dimethyl-pyridinemol) and 100 mls. of acetonitril are mixed. To the mixture is added indrops, whilst stirring, 11.4 gs. of his(N,N-dimethyl-amido)-phosphorylchloride mol). After the acid chloridehas been added completely, stirring is continued at room tempera turefor seven hours. Then the acetonitril is distilled 01f in vacuo. Theresidue is extracted with acetone. The solution thus obtained wasevaporated; the crystalline residue is extracted with benzene. Thebenzene is evaporated and the crystalline product obtained isrecrystallized twice from ligroine. The analysis exhibits that equimolarquantities of starting material have reacted with one another. Yield:50%. Melting point 92 to 95 C.

Analysis.-Calculated: P=12.58%; C=39.02%; H =7.78%; N=34.'12%. Found: P=12.7%; C=36.89%; 36.76%; H=7.71%; 7.97%; N=33.78%; 34.22%.

EXAMPLE IV 13 gs. of 5-(1'-methylethyl)-3-amino-triazol-1,2,4 (0.1 mol)(Reilly, Drumrn: J. Chem. Soc. (1926) page 1731), 20 gs. of his(N,N-dimethylamido) phosphorylchloride (0.12 mol) and 12.1 gs. oftriethylamine (0.12 mol) are mixed with mls. of acetonitril. The mixtureis heated, whilst stirring at 60 to -65 C. for five hours. The solventis then distilled ofi? in vacuo. The residue is extracted with acetone.The acetonic solution is inspissated in vacuo and the residue is twicerecrystallized from ligroine and once from carbon disulphide. Yield 50%.Melting point 101 to 105 C. For analyzing purpose a small quantity ofsubstance is recrystallized from carbon disulphide. Melting point 105 to106 C.

Analysis.Calculated P=1l.90%; C:41.53%; H =8.13%; N=32.29%. Found:P=12.1%; C=40.95%; 41;.11%; H=8.32%; 8.20%; N=33.49%; 33.96%.

EXAMPLE V To a mixture of 30.8 gs. of 5-n-pentyl-3-amino-triazol- 1,2,4(0.2 mol) (Kaiser, Peters: Journal Org. Chem. 18, page 196 (1953)), 18.6gs. of collidine (0.2 mol) and 200 mls. of acetonitril is added indrops, at normal temperature whilst stirring, 42.5 gs. of his(N,N-dimethylamido)-phosphorylchloride (0.25 mol). Then the mixture isheated at 60 to 70 C. for three and a half hours. When adding acetone,the hydrochloric acid salt of collidine is separated out. It is filteredoff. The filtrate is inspissated in vacuo; the residue extracted withbenzene, the benzene solution washed, in succession, with 0.5 Nhydrochloric acid, water, a solution of sodium bicarbonate and finallyagain water. The solution is then dried and inspissated. The residue, acrystalline mass, is recrystallized four times from petroleum ether.Yield 47%. Melting point 49 to 53 C. For analyzing purposes a smallquantity is recrystallized again from petroleum-ether. Melting point 52to 53 C.

Analysis.Calculated: P=10.74%; C:'45.82%; H =8.74%; N=29.15%. Found:P:-11.'0-%; C=45.77%; 45.57%; H=8.89%; 8.75%; N=28.98%; 28.97%.

EXAMPLE VI A mixture of 86 gs. (0.5 mol) of arnino-guanidine bisulphate(melting point 158 to 160 C.), 72 gs. of caprylic acid (0.05 mol), 20mls. of water and a few drops of concentrated nitric acid (s.w. 1.4) isheated on an oil bath at 130 to 140 C. for 50 hours.

The reaction mixture is poured out in 200' mls. of water after thereaction was terminated, in a porcelain dish; it is neutralized with 60gs. (more than 0.5 mol) of anhydrous sodium carbonate until the reactionwas weak alkaline and the mixture was evaporated to dryness. Thesemisolid mass obtained is extracted with dry benzene and the benzene isdistilled oif. The crude substance is converted into the nitric acidsalt and recrystallized from water. The melting points of the nitrate is147 C.; with the calculated quantity of methanolic potassium hydroxidesolution this nitrate is converted into the free base, which is finallycrystallized from ethyl-acetate. The yield is 1.5 gs.= 16% of3-amino-5-heptyl-triazol-1,2,4; melting point 120 to 125 C.

Analysis. Calculated: C=59.30%; H=9.95%; N =30.74%. Found: C=59.64%;59.37%; H=9.95%; 9.87%; N== 3l.1 1%; 30.80%.

Remark: For analyzing purposes a small quantity of the substance Wasrecrystallized from a mixture of alcohol and Water (1:5); Melting point134 to 134.5 C. 9.1 gs. of 5-n-heptyl-3-amino-triazol-1,2,4 mol), 4.6gs. of a mixture of w, 18- and 'y-picoline mol), 8,5 gs. of bis (N,N-dirnethylamido)-phosphoryl-chloride 5 mol) and 50 mls. of diethylether are heated at 60 to 70 C. Whilst stirring, for 6 hours. Then theacetonitril is evaporated in vacuo. The residue is extracted with ether.The ethereal solution is Washed with 0.5 N hydrochloric acid and thenwith water. The solution is dried and the ether evaporated. The residueis purified via alumina. A yellow oil is obtained. Yield 31%.

Analysis-Calculated: P=9.79%; C=49.35 H-= 9.24%; N=26.56%. Found:P=9.4%; C=48.76%; 48.61%; H=9.34%, 9.49%; N:26.40%, 26.21%.

EXAMPLE VII 86 gs. (0.5 mol) of amino-guanidine bisulphate (meltingpoint 158 to 160 C.) is heated on an oil bath with 100 gs. of lauricacid (0.5 mol) at 150 to 160 C., for 30 hours. After the termination ofthe reaction the viscous, solid contents of the reaction vessel aretransferred with water to a porcelain dish and neutralized withanhydrous sodium carbonate. On the vapour bath the solution isevaporated to dryness. The last remains of Water are removed in thevacuum drying chamber,

after which the dry substance is pulverized and extracted with absolutealcohol. After cooling the sodium laurate crystallizes which emanatesfrom the unconverted lauric acid, the laurate is filtered 01f. Thefiltrate is inspissated and the solid residue obtained is recrystallizedtwice from ethyl-acetate. The yield is 38 gs.=32% of -undecyl-3-amino-triazol-1,2,4; melting point 128 to 131 C.

Analysis.--Calculated: C=65.50%; H=10.96%; N: 23.50%. Found: C=65.43%,65.15%; H=11.l6%, 11.00%; N=23.74%, 23.73%.

Remark: A supply of the substance was recrystallized from ethyl-acetate.Melting point: 131 to 132 C. (for analyzing purposes).

A mixture of 5.7 gs. of bis(N,N-dimethylamido)phos phorylchloride mol)7.9 gs. of 5-undecyl-3-animotriazol-1,2,4 mol), 5.3 gs. of2,6-diethyl-pyridine mol) and 75 mls. of benzene are heated at 70 to C.whilst continuously stirring, for 5 hours. Upon cooling the hydrochloricacid salt of 2,6-diethyl-pyridine is separated out. It is filtered off.The filtrate is washed, in succession, with water, a solution of sodiumbicarbonate and again Water. The solution is dried and the benzeneevaporated in vacuo. The crystalline residue is recrystallized fromether. Yield 45%. Melting point 46.5 to 47.5 C.

Analysis.-Calculated: P=8.31%; C=54.81%; H: 10.01%; N=22.56%. Found:P-=8.6%; C=55.07%, 54.61%; H=10.19%, 10.05%; N=22.33%, 22.52%.

EXAMPLE VIII 8 gs. of 5-phenyl-3-amino-triazol-1,2,4 mol) (Benack,Dissert. Miinchen 1896), 6.0 gs. of collidine mol) 8.5 gs. ofbis(N,N-dimethylamido) phosphorylchloride mol) and 50 mls. ofacetonitril are mixed and heated at 60 to 70 C., whilst stirring, for 10hours. Then the acetonitril is removed by distillation in vacuo. Theresidue is extracted with benzene. The solution obtained is evaporatedin vacuo. The remaining crystalline mass is recrystallized from aqueousalcohol. Yield 71%. Melting point 167.5 to 168 C.

Analysis.Calculated: P=10.52%; C=48.97%; H: 6.51%; N=28.56%. Found:P=10.7%; C=49.03%, 49.21%; H=6.51%, 6.55%; N=28.58%, 28.61%.

EXAMPLE IX A mixture of 86 gs. (0.5 mol) of amino-guanidine bisulphate(melting point 158 to 160 C.), 68 gs. (0.5 mol) of phenyl-acetic acid, 5mils. of water and a few drops of concentrated nitric acid is heated inan oil bath at to C., for 30 hours. After the termination of thereaction the clear solution is transferred with about 70 mls. of waterto a porcelain dish, neutralized with 55 gs. of anhydrous sodiumcarbonate until the reaction was weak alkaline. The solution obtained isevaporated to dryness and then extracted With, in total, 30 mls. ofabsolute alcohol. After filtration the alcohol is distilled off and theresidue is crystallized from Water. The yield is 36 gs.= 41% of3-amino-5-benzyl-triazol-1,2,4; melting point 170 to 170.3 C.

A nalysis.-Calculated 32.16%. Found: C:62.52%, 5.59%; N=32.28%, 32.32%.

Whilst stirring, a mixture of 11.6 gs. of 5-benzyl-3-amino-triazol-1,2,4 mol), 8.1 gs. of collidine mol), 11.4 gs. ofbis(N,N-dimethylamido)-ph0sporylchloride mol) and 75 mls. of acetonitrilis heated at 70 C. for 8 hours. The solvent is then evaporated in vacuo.The residue is extracted with benzene. The extract is inspissated invacuo; a crystalline substance is left. This crystalline product isrecrystallized from aqueous alcohol. The substance crystallizes with 1mol of crystal water. Yield 60%. Melting point 107 to 108 C. Theanhydrous substance melts at 130.5 to 131 C.

Analysis.Calculated: P=9.49%; C=47.84%; H: 7.10%; N=25.75%. Found:P=9.6%, 9.9%; C: 47.8%, 47.75%; H:7.26%, 7.26%;N=25.32%, 25.32%.

EXAMPLE X A mixture of 86 gs. (0.5 mol) of amino-guanidine bisulphate(melting point 158 to 160 C.), 68 gs. (0.5 mols) cinnamic acid (0.5 mol)5 mls. of water and a few drops of concentrated nitric acid is heated inan oil bath at to C., for 50 hours. The mixture is then transferred with15 0 mls. of water to a poreclain dish, neutralized with anhydroussodium carbonate and evaporated to dryness on a vapour bath. The drymass is extracted with absolute alcohol, the alcohol is distilled offpartly and after the addition of ethyl-acetate, the basis is convertedinto the nitrate. The melting point of the nitrate is, afterrecrystallisation from water, about 260 C. The free base is obtainedtherefrom by means of the calculated quantity of methanol/KOH. Thesubstance is recrystallized from C:62.05%; III-5.78; N: 62.41%; H:5.96%,

13 The yield is 5 gs.=5% of 3- methanol/water (2:5).amino-S-styryl-triazol-1,2,4; melting point 233.5 C.

AnaIysis.Calculated: C:64.49%; H=5.41%; N: 30.09%. Found: C:64.33%,64.54%; H:5.53%, 5.57%; N:29.84%, 29.87%.

4.9 gs. of 3-arnino-5-styryl-triazol-1,2,4 (0.026 mol), 3.2 gs. ofcollidine (0.026 mol), 4.5 gs. of bis(N,N-dimethylamido)phosphorylchloride (0.026 mol) and 50 mls. of acetonitril are heated,whilst stirring, at 60 to 70 C. for 17 hours. Then the acetonitril isdistilled off in vacuo. The residue is extracted with benzene. Thecrystalline substance, which separates out during the dis tillation ofbenzene, is isolated by filtration and recrystallized from ligroine.Yield 58%. Melting point 149.5 to 152.5 C.

Analysis.Calculated: P=9.67%; C=52.49%; H: 6.61%; N=26.23%. Found:P=10.0%; C=52.44%, 52.46%; H=6.77%, 6.64%; N=25.87%, 25.95%.

EXAMPLE XI To a mixture of 4.2 gs. of 3-amino-triazol-1,2,4 (44 mol) 6.0gs. of collidine mol) and 50 mols. of acetonitril is added 11.3 gs. ofbis(N,N-diethylamido)phosphorylchloride 0/ mol). The mixture obtained isheated at 70 to 80 C., Whilst stirring, for 7 hours. Then theacetonitril is evaporated in vacuo. The residue is extracted withbenzene. The solution in benzene is inspis sated; the mass obtained isrecrystallized from water. Yield 53%. Melting points 105 to 106 C. Foranalyzing purpose a small quantity is recrystallized from water. Meltingpoint 106 to 106.5 C.

Analysis.Calculated: P=11.29%; C=43.78%; H: 8.45%; H:30.64%. Found:P:11.3%; C:43.66%, 43.61%; H=8.65%, 8.70%; N=30.11%, 30.36%.

EXAMPLE XII 6.3 gs. of bis(N,N-diethylamido)phosphorlychloride (0.28mol) is added, whilst stirring, to a mixture of 4.2 gs. of5-n-pentyl-3-amino-triazol1,2,4 (0.28 mol) 3.4 gs. of collidine (0.28mol) and 40 mls. of ether. The mixture is heated at 70 to 75 C., whilststirring, for 6 hours. Then the acetonitril is removed by distillationin vacuo and the residue is extracted with ether. The ethereal solutionis washed with water, dried and inspissiated. The residue is dissolvedin petroleum ether. This solution is washed with water and after drying,it is inspissated. An oil is obtained, which crystallizes after sometime. Yield 87%.

Analysis.Calculated: P=8.99%. Found: P=9.1%.

EXAMPLE XIII A mixture of 16.8 gs. of 3-amino-triazol-1,2,4 (2.10 mol),18.65 gs. of bis (N,N-dimethylamido)thiophosphorylchloride mol) and 300mls. of acetonitril is heated at 65 to 70 C., whilst continuouslystirring, for 8 hours. The acetonitril is then removed by distillationin vacuo. To the solid residue water is added. The part not soluble inWater is filtered oil? and crystallized from Water. Yield 22%. Meltingpoint 120 to 121 C.

Analysis. Calculated: P 13.22%; S 13.68%. Found: P=13.1%; S=13.5%.

EXAMPLE XIV In 25 mls. of anhydrous pyridine is dissolved 7.7 gs. of3-amino-S-n-pentyltriazol-1,2,4 (0.05 mol). To the solution is added indrops 9.3 gs. of his (N,N-dimethylamido) thio-phosphorylchloride (0.05mol). The mixture is then evaporated in vacuo and to the residue wateris added. The oil obtained is extracted with ether. The ethereal extractis Washed with water, dried and inspissated. The residue is acrystalline product. Yield 65%. Melting point 139 to 140 C.

Analysis. Calculated: P 10.18%; C 43.40%; H=8.2S%;N=27.61%;S=10.53%.Found: P:10.3%; C=43.90%, 43.51%; H=8.32%, 8.31%; N=26.35%, 26.89%;S=10.67%, 10.63%.

1 4 EXAMPLE XV 7.78 gs. of 5-(4'-chloro-phenyl)-3-amino-triazol-1,2,4(0.04 mol) (Hoggarth, J. Chem. Soc. (1950) 612), 4.84 gs. of collidine(0.04 mol) and 6.82 gs. of bis(N,N-dimethylamido)-phosphorylchloride aremixed With 100 mls. of acetonitril. The mixture is stirred at atemperature between 70 and C. for six hours. Then the acetonitril isevaporated in vacuo. The residue is extracted a few times with hotbenzene. The benzene is evaporated; the crystalline product obtained isrecrystallized from a mixture of ethanol and water. Yield: 73%. Meltingpoint: 170 to 171 C.

Analysis.Calc.: C=43.84%; H=5.52%; N=25.56%; Cl=10.79%; P=9.42%. Found:C=44.20%, 44.50%; I-I=5.81%, 5.88%; N=26.17%, 26.33%; Cl=11.03%, 11.11%;P=9.4%.

EXAMPLE XVI 5.7 gs. of 5-(4'-methoxyphenyl)-3-amino-triazol-l,2,4 (0.03mol) (Hoggarth, J. Chem. Soc. (1950) 612), 4 gs. of collidine (0.03 mol)and 5.1 gs. of bis (N,N-dimethylamido)-phosphorychloride (0.03 mol) arejoined in 100 mls. of acetonitril. The mixture is then stirred at atemperature of 75 to C. for six hours. Then the acetonitril is removedby evaporation in vacuo. The residue is extracted a few times with drybenzene. The benzene is evaporated and the remaining crystalline productis recrystallized from a mixture of water and alcohol (1:3). Yield: 72%.Melting point 173 to 174 C.

Analysis. Calculated: C 48.14%; H 6.52%; N=25.91%; P=9.55%'. Found:C=48.46%, 48.64%; H=6.58%, 7.11%; N=25.50%, 25.52%; P=9.55%.

EXAMPLE XVII 7.8 gs. of 5-carbaethoxy-3-amino-triazol-1,2,4 (0.05 mol)(Thiele Manchot, Ann., 303 54 (1898)) 6.0 gs. of collidine (0.05 mol)and 8.5 gs. of his (N,N-dimethyl amido)-phosphorylchloride (0.05 mol)are mixed with mls. of acetonitril. The mixture is heated, Whilststirring, at 50 to 60 C. for 24 hours. Then the acetonitril is removedby evaporation. The residue is extracted with cold Water and then with amixture of acetone and ethanol. The acetone and the ethanol areevaporated. The remaining crystalline product is recrystallized fromWater. Yield: 51%. Melting point 151 to 153 C.

Analysis. Calculated: P 10.67%; C 37.24%; H=6.60; N=28.95%. Found:P=10.3%; C=36.61%, 36.64%; H=6.57%, 6.59%; N=28.94%, 29.16%.

EXAMPLE XVIII 23.6 gs. of 3-amino-triazol-1,2,4-carboxylic acid-5 (0.185mol) is dissolved in 75 mls. of n-pentanol. Dry HCl gas is passedthrough the solution; then the solution is boiled for 6 hours. Then-pentanol is removed by evaporation in vacuo. The residue is extractedwith cold Water and then crystallized from a mixture of ethanol andWater. Yield: 26%. Melting point 168 to 169 C.(5-carb-n-pentoxy-3-amino-triazol-1,2,4)

Analysis.-Calc.: C:48.47%; H:7.12%; N:28.27%. Found: C:46.92%, 47.20%;H:7.37%, 7.30%; N:27.63%, 27.35%.

7.92 gs. of 5-carb-n-pentoxy-3-amino-triazol-1,2,4 (0.04 mol) 4.82 gs.of collidine and 6.82 gs. of his (N,N-dimethyl-amido)-phosphorylchloride (0.04 mol) are mixed With 75 mls. ofacetonitril. The mixture is heated, whilst stirring, at 70 C. for sixhours. The acetonitril is removed by evaporation in vacuo. The residueis suspended in water. The crystalline product is filtered off andrecrystallized from vligroin. Yield: 45%. Melting point to 107 C.

Analysis. Calculated: P:9.32%; C:43.37%; H:7.59%; N:25.29%. Found:P:9.27%; C:43.94%, 43.65%; H:7.65%, 7.65%; N:26.31%, 26.34%.

' Found:

1 5 EXAMPLE XIX 25.6 gs. of 3-amino-triazol-1,2,4-carboxylic acid 5 (0.2mol) is mixed with 100 mls. of isopropanol. Dry HCl gas is passedthrough the mixture; then the mixture is boiled for 12 hours. Theisopropanol is removed by evaporation in vacuo. The residue is dissolvedin a small quantity of water and neutralized with sodium carbonate. Theisopropyl-ester is precipitated and filtered off. Yield: 34%. Meltingpoint 253 to 254 C. (5-carb-isopropoxy-3amino-triazol-1,2,4).

Analysis.Calc.: C:42.35%; H:5.91%; N:32.92%. C:42.49%, 42.52%; H:5.88%,5.96%; N:32.91%, 33.19%.

11.9 gs. of S-carrb-isopropoxy 3 amino-triazol-1,2,4 (0.07 mol), 8.1ags. of collidine A mol) and 75 mls. of acetonitril are mixed. Whilststirring the mixture has added to it 12.0 gs. of bis(N,N-dimethyl-amido)phosphorylchloride. The mixture is heated at atemperature of 70 to 80 C. for 10 hours. The acetonitril is removed byevaporation. The residue is suspended in water. The crystalline productis filtered off and recrystallized from water. Yield: 59%. Melting point181 to 182 C.

Analysis. Calc.: C::39.47%; H:6.96%; N:27.62%; P:10.18%. Found:C:39.46%, 39.88%; H:7.14%, 7.19%; N:26.68%, 26.91%; P:10.18%.

EXAMPLE XX In a solution of 2.3 gs. of sodium (0.1 mol) in 65 mls. ofmethanol is dissolved 15.4 gs. of 5-pentyl-3-aminotriazol-1,2,4 (0.1mol). Then 20 gs. of bis (N,N-dimethylamido) phosphorylchloride is addedin drops. Then the mixture is stirred for 25 hours at a temperature ofabout 80 C. After cooling the formed NaCl is filtered off; the filtrateis concentrated by evaporation and the residue received in ether. Theethereal solution is washed three times with a small quantity of water,dried on sodium sulphate and concentrated by evaporation. The residue isrecrystallized from a mixture of petroleum ether (boiling range 40 to 60C.) and ether (3-1). Yield: 15.9 gs. (55%). Melting point 51 to 53 C.

EXAMPLE XXI In a solution of 2.3 gs. of sodium (0.1 mol) in 100 mls. ofmethanol is dissolved 16.0 gs. of 5-phenyl-3- amino-triazol-1,2,4 (0.1mol). The methanol is evaporated in vacuo and the remaining salt issuspended in 80 mls. of acetonitril. To the suspension is added 20 gs.of bis (N,N-dimet-hyl-amido) phosphorylc-hloride. The mixture is thenheated whilst stirring, for 2.5 hours at 80 to 85 C. The solution isfiltered hot and the filtrate is concentrated by evaporation. Theresidue, a crystalline product, is recrystallized from a mixture ofethanol and water (1:3). Yield: 23.4 gs. (80%). Melting point 167 to 168C.

EXAMPLE XXII In 55 mls. of anydrous ethanol are dissolved 2 gs. of NaOHmol) and 8 gs. of 5-phenyl-3amino-triazol- 1,2,4 mol). To the solutionis added 10 gs. of his (N,N-dimethylamido)phosphorylchloride at atemperature of to C. The reaction mixture is then stirred at 0 to 5 C.for four hours. The NaCl obtained is filtered off. The filtrate isconcentrated by evaporation and the residue is recrystallized from amixture of alco- 1101 and water (1-3). Yield: 10.8 gs. (73%). Meltingpoint 167 to 168 C.

EXAMPLE XXIII 4 gs. of 5-phenyl-3amino-triazol-1,2,4 4 mol) is dissolvedin a solution of 1. g. of soduim hydroxide 4 mol) in 20 mls. ofmethanol. To the solution is added dripwise, whilst stirring, 5 gs. ofhis (N,N-dimethyl- .amido) phosphoryl chloride at a temperatureof aboutC. Then stirring is continued for one hour at a temperature between "-10and 10 C. The reaction mixture is filtered and the methanol removed byevaporation in vacuo. The crystalline product is suspended in 50 mls. of0.5 N-caustic soda lye and then filtered off. Yield: 81%. Melting point165 to 166 C.

EXAMPLE XXIV 4 gs. of 5-phenyl-3-aminotriazol-1,2,4 4 mol) is introducedinto a suspension of 7.96 gs. of Ba(OH 8H O in 50 mls. of ethanol. Tothe mixture is added dripwise 5 gs. of his(N,N-dimethylamido)phosphorylchloride at a temperature of about 10 C.The mixture is then stirred for three hours. The deposit obtained isfiltered off and the solution is concentrated by evaporation in vacuo.The crystalline residue is suspended in 50 mls. of 0.5 N-caustic sodaand then filtered 01f. Yield: 70%. Melting point 166 to 167 C.

EXAMPLE XXV In 25 mls. of ethanol are introduced 1 g. of NaOH 4 mol) (asa 50% solution in water) and 4 gs. of 5- phenyl-3-am-ino-triazol- 1,2,4mol). Then at a temperature between 0 and 5 C., 5 gs. of bis(N,N-dimethylamido)phosphorylchloride is added dropwise. The solution isthen stirred further for three hours at the same temperature. The NaClis filtered off, the filtrate is concentrated .by evaporation and theresidue is crystallized from a mixture of ethanol and Water (1-3).Yield: 5.2 gs. (71%). Melting point 167 to 168 C.

EXAMPLE XXVI Into 35 gs. of anhydrous ethanol are introduced 1.0 g. ofNaOH 4 mol) (as a 50% solution in water) and 3.85 gs. of5-pentyl-3-amino-triazol-1,2,4 4 mol). At a temperature between 0 and 5C. is added dripwise 5 gs. of his(N,N-dimethylamido)-phosphorylchloride. The mixture is then stirredfurthermore for 2.5 hours at the same temperature. The NaCl obtained isfiltered off and the filtrate is concentrated by evaporation. Theresidue is dissolved in ether and the solution in ether is washed threetimes with a small quantity of water (until the reaction is neutral).The ethereal extract is dried and concentrated by evaporation. Yield:6.76 gs. (94% Melting point 42 to 49 C. After a double crystallization,once from petroleum ether (40 to 60) and once from a mixture ofpetroleum ether (boiling range 40 to 60 C.) and ether (21) a meltingpoint of 51 to 52 C. is reached.

EXAMPLE XXVII Into 50 mls. of 50% by weight solution of KOH in water issuspended 4 gs. of 5-phenyl-3amino-tri-azol-1,2,4 mol). To thesuspension is added dripwise, at 50 C. to 10 C., 5 gs. of bis(N,N-dimethylamido)phosphorylohloride, after stirring is continued for2.5 hours at the same temperature. The reaction mixture is diluted withmls. of water and the product separated out is filtered off. Yield: 5.63gs. (77%). Melting point 166 to 167 C.

EXAMPLE XXVIII In '50 mls. of water are dissolved 2 gs. of NaOH /go mol)and 8 gs. of 5-phenyl-3amino-triazol-1,2,4 mol). To the solution thusobtained is added 10 gs. of bis (N,N-dimethylamido)phosphorylchloride ata temperature between 0 and 5 C., after which stirring is continued for2.5 hours. The precipitate is filtered off and extracted withchloroform. The residue is 5-phenyl-3- amino triazol-1,2,4. Yield: 5.85gs. (73%). Melting point 184 to 187 C.

The solution in chloroform is concentrated by evaporation; the residueis crystallized from a mixture of ethanol and water (1-3). Yield: 0.78gs. (5.3%). Melting point to 167 C.

EXAMPLE XXIX 8 gs. of 5phenyl-3-amino-triazoll,2t4 (0.05 mol) and 50mls. of 30% by weight of sodium hydroxide are joined. To the mixture isadded dripwise, whilst stirring, 10 gs. of ibis(N,Ndimethylamido)-phosphorylchloride at a temperature of 5 to 10 C. Thewhole mixture is then stirred again for 1.5 hours at a temperature ofabout C. Then 100 mls. of water is added. The precipitated crystallineproduct is filtered off. Yield: 22%. Melting point 166 to 167 C.

What we claim is:

1. A method of combatting plant destructive insects, mites and fungiwhich comprises treating living plants with a pesticidally effectiveamount of an a-minotriazole phosphorus compound of the formula:

wherein R R R R are each alkyl of from 1 to 5 carbon atoms, X is abivalent atom selected from the group consisting of sulfur and oxygen, Ris 3-aminotriazole 1,2,4 wherein the 5 carbon is directly joined to amember of the group consisting of hydrogen, phenyl, 4-chloro-phenyl,4-meth0xy phenyl, styryl, alkyl of 1-8 carbon atoms and carbo-loweralkoxy and wherein the phosphorus is joined directly to a ring nitrogenof the triazole moiety.

2. A method of combatting plant destructive insects, mites and fungiwhich comprises treating living plants with a pesticidally effectiveamount of his (dimethylamido) phosphoryl-5-phenyl-3-aminotriazole-1,2,4wherein the phosphorus is directly attached to a ring nitrogen.

3. A method of combatting plant destructive insects, mites and fungiwhich comprises treating living plants with a pesticidally effectiveamount of his (dimethylamido) phosphoryl 5 npentyl-3-aminotriazole-1,2,4 wherein the phosphorus is directly attachedto a ring nitrogen.

4. A method of combatting plant destructive insects, mites and fungiwhich comprises treating living plants with a pesticidally effectiveamount of his (dimethylamido) phosphoryl-5-ethyl-3-aminotriazole-1,2,4wherein the phosporus is directly attached to a ring nitrogen.

5. A method of combatting plant destructive insects, mites and fungiwhich comprises treating living plants with a pesticidally effectiveamount of his (dimethylamido) phosphoryl 5isopropyl-3-aminotriazole-1,2,4 wherein the phosphorus is directlyattached to ring nitrogen.

6. A method of combatting plant destructive insects, mites and fungiWhich comprises treating living plants with a pesticidally effectiveamount of his (dimethylamido) phosphoryl-5-methyl-3-aminotriazole-1,2,4Wherein the phosphorus is directly attached to a ring nitrogen.

7. A method of combatting plant destructive insects, mites and fungiwhich comprises treating living plants with a pesticidally effectiveamount of his (dimethylamido) phosphoryl 5 Itheptyl-3-arninotriazole-1,2,4 wherein the phosphorus is directlyattached to a ring nitrogen.

8. A method of combatting plant destructive insects, mites and fungiwhich comprises treating living plants with a pesticidally effectiveamount of his (dimethylamido) phosphoryl-5-benzyl-3-aminotriazole-1,2,4wherein the phosphorus is directly attached to a ring nitrogen.

9. A method of combatting plant destructive insects, mites and fungiwhich comprises treating living plants with a pesticidally effectiveamount of his (dimethylamido) phosphoryl 3 aminotriazole 1,2,4 whereinthe phosphorus is directly attached to a ring nitrogen.

10. A method of combatting plant destructive insects, mites and fungiwhich comprises treating the living plants with a pesticidally effectiveamount of his (dimethylamido) thionophosphoryl-S-n-pentyl 3aminotriazole- 1,2,4 wherein the phosphorus is directly attached to aring nitrogen.

References Cited by the Examiner UNITED STATES PATENTS 2/1964 Koopmanset al. 260-308 OTHER REFERENCES Elings, H: Experiences with5-amino-3-phenyl-l-bis (dimethylamido) phosphoryl-1,2,4-triazole, a newfungicide controlling powdery mildew: Proc. Brit. Insecticide FungicideConf. Brighton, Engl. 1961, pp. 451-9 (Pub. 1962); Abstracted in Chem.Abstracts 57: 17129c Dec. 24, 1962.

Koopmans, M. 1.: Systemic fungicidal action of some 5aminol-bis(dimethylamido)phosphoryl 1,2,4 triazoles Mededel.Landbouwhogeschool Opzoekings as. Staat Gent. 25: 1221-6 (1960);abstracted in English in Chem. Abstracts 57: 1326b, July 9, 1962.

Van den Bos et al.: Investigations on pesticidal phosphorus compounds.I. Fungicides, insecticides, and acaricides derived from3-amin0-1,2,4-triazole. II. The structure of phosphorus compoundsderived from 3- amino-1,2,4-triazole. III. The structure of the reactionproduct of 3-amino-5-phenyl-1,2,4-triazole andbis(dimethylamido)phosphoryl chloride. Rec. trav. ohim. 79: 807-822;836-852; 1129-1136 (1960); ibid., IV), Rec. trav. chim. 80: 1040-1047(1961).

LEWIS GQTTS, Primary Examiner.

1. A METHOD OF CONBATTING PLANT DESTRUCTIVE INSECTS, MITES AND FUNGIWHICH COMPRISES TREATING LIVING PLANTS WITH A PESTICIDALLY EFFECTIVEAMOUNT OF AN AMINOTRIAZOLE PHOSPHORUS COMPOUND OF THE FORMULA: